全文获取类型
收费全文 | 2216篇 |
免费 | 74篇 |
国内免费 | 4篇 |
专业分类
化学 | 1563篇 |
晶体学 | 7篇 |
力学 | 40篇 |
数学 | 326篇 |
物理学 | 358篇 |
出版年
2024年 | 4篇 |
2023年 | 14篇 |
2022年 | 75篇 |
2021年 | 70篇 |
2020年 | 51篇 |
2019年 | 56篇 |
2018年 | 48篇 |
2017年 | 33篇 |
2016年 | 95篇 |
2015年 | 68篇 |
2014年 | 77篇 |
2013年 | 105篇 |
2012年 | 164篇 |
2011年 | 188篇 |
2010年 | 145篇 |
2009年 | 92篇 |
2008年 | 144篇 |
2007年 | 171篇 |
2006年 | 109篇 |
2005年 | 96篇 |
2004年 | 87篇 |
2003年 | 62篇 |
2002年 | 44篇 |
2001年 | 15篇 |
2000年 | 24篇 |
1999年 | 26篇 |
1998年 | 18篇 |
1997年 | 16篇 |
1996年 | 21篇 |
1995年 | 26篇 |
1994年 | 19篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1977年 | 4篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1905年 | 3篇 |
排序方式: 共有2294条查询结果,搜索用时 15 毫秒
41.
We studied the thermal diffusion behavior of poly(N-isopropylacrylamide) (PNiPAM) in ethanol in a temperature range from T = 14.0 degrees C to T = 40.0 degrees C by means of thermal diffusion forced Rayleigh scattering. The obtained Soret coefficient S(T) of PNiPAM was positive for lower temperatures (T < 34 degrees C), while S(T) showed a negative value for higher temperatures (T > 34 degrees C). This means PNiPAM molecules move to the cold side for temperatures T < 34 degrees C, whereas they move to the warm side for T > 34 degrees C. This is the first nonaqueous polymeric system for which a sign change with temperature has been observed. We performed static and dynamic light scattering experiments in the same temperature range. The second virial coefficient determined from dilute solutions by static light scattering (SLS) was positive in the comparable temperature range. The results of SLS for the semidilute solution showed a strong repulsion among PNiPAM chains which was enhanced by increasing temperature. These results imply that the observed thermally induced sign change of S(T) does not depend on the intermolecular interactions among PNiPAM chains. 相似文献
42.
Ana Cristina Gmez-Herrero Carlos Snchez-Snchez Frdric Chrioux Jose Ignacio Martínez Jos Abad Luca Floreano Alberto Verdini Albano Cossaro Estelle Mazaleyrat Valrie Guisset Philippe David Simone Lisi Jos Angel Martín Gago Johann Coraux 《Chemical science》2021,12(6):2257
Catechols are ubiquitous substances often acting as antioxidants, thus of importance in a variety of biological processes. The Fenton and Haber–Weiss processes are thought to transform these molecules into aggressive reactive oxygen species (ROS), a source of oxidative stress and possibly inducing degenerative diseases. Here, using model conditions (ultrahigh vacuum and single crystals), we unveil another process capable of converting catechols into ROSs, namely an intramolecular redox reaction catalysed by a Cu surface. We focus on a tri-catechol, the hexahydroxytriphenylene molecule, and show that this antioxidant is thereby transformed into a semiquinone, as an intermediate product, and then into an even stronger oxidant, a quinone, as final product. We argue that the transformations occur via two intramolecular redox reactions: since the Cu surface cannot oxidise the molecules, the starting catechol and the semiquinone forms each are, at the same time, self-oxidised and self-reduced. Thanks to these reactions, the quinone and semiquinone are able to interact with the substrate by readily accepting electrons donated by the substrate. Our combined experimental surface science and ab initio analysis highlights the key role played by metal nanoparticles in the development of degenerative diseases.An antioxidant catechol transforms following intramolecular redox reactions into highly reactive oxygen species, a semiquinone and a quinone, on copper. 相似文献
43.
Ultraviolet (UV) spectrophotometric and nonaqueous volumetric methods are described for the determination of carvedilol in pharmaceutical formulations. Linearity, precision, and accuracy were evaluated according to the validation guidelines of the International Conference on Harmonization and the United States Pharmacopeia for both methods. The UV spectrophotometric procedure was performed in ethanol at 244 nm. Good linearity was obtained between 2 and 7 microg/mL with a correlation coefficient of 0.9999. The intra- and interday precision values were <2% for all samples analyzed. The accuracy, determined from recovery studies, was between 97.5 and 102.2%. The other procedure was based on the volumetric quantitation of carvedilol in a nonaqueous medium with 0.01 M perchloric acid and 1% violet crystal as the indicator. The validation of the volumetric method yielded good results that included linearity (r of > 0.999), precision (relative standard deviations of <2% for intra- and interday precision), and accuracy (96.4-102.4%). The methods were applied to tablets and compounded capsules. Statistical analysis by analysis of variance showed no significant difference between the results obtained by the proposed methods. 相似文献
44.
Michela Iezzi Simone 《Tetrahedron letters》2005,46(34):5761-5765
Efficient SN2 ring closure of open chain trihydroxytriflates—in which the leaving group is on a primary carbon adjacent to a quaternary centre—provides access to tetrahydrofurans with branched carbon chains from branched carbohydrate lactones; the first examples of a new class of branched chain tetrahydrofuran α,α-disubstituted-δ-sugar amino acid scaffolds are described. 相似文献
45.
Fábio C. Sampaio Paolo Torre Flávia M. Lopes Passos Célia Alencar de Moraes Patrizia Perego Attilio Converti 《Applied biochemistry and biotechnology》2007,136(2):165-181
To obtain in-depth information on the overall metabolic behavior of the new good xylitol producer Debaryomyces hansenii UFV-170, batch bioconversions were carried out using semisynthetic media with compositions simulating those of typical acidic
hemicellulose hydrolysates of sugarcane bagasse. For this purpose, we used media containing glucose (4.3–6.5 g/L), xylose
(60.1–92.1 g/L), or arabinose (5.9–9.2 g/L), or binary or ternary mixtures of them in either the presence or absence of typical
inhibitors of acidic hydrolysates, such as furfural (1.0–5.0 g/L), hydroxymethylfurfural (0.01–0.30 g/L), acetic acid (0.5–3.0
g/L), and vanillin (0.5–3.0 g/L). D. hansenii exhibited a good tolerance to high sugar concentrations as well as to the presence of inhibiting compounds in the fermentation
media. It was able to produce xylitol only from xylose, arabitol from arabinose, and no glucitol from glucose. Arabinose metabolization
was incomplete, while ethanol was mainly produced from glucose and, to a lesser less extent, from xylose and arabinose. The
results suggest potential application of this strain in xyloseto-xylitol bioconversion from complex xylose media from lignocellulosic
materials. 相似文献
46.
Frank Seela Simone Budow Henning Eickmeier Hans Reuter 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(1):o54-o57
The title compound, 4‐amino‐1‐(2‐deoxy‐β‐d ‐erythropentofuranosyl)‐5‐(prop‐1‐ynyl)pyrimidin‐2(1H)‐one, C12H15N3O4, shows two conformations in the crystalline state which differ mainly in the glycosylic bond torsion angle and the sugar pucker. Both molecules exhibit an anti glycosylic bond conformation, with torsion angles χ = −135.0 (2) and −156.4 (2)° for molecules 1 and 2, respectively. The sugar moieties show a twisted C2′‐endo sugar pucker (S‐type), with P = 173.3 and 192.5° for molecules 1 and 2, respectively. The crystal structure is characterized by a three‐dimensional network that is stabilized by several intermolecular hydrogen bonds between the two conformers. 相似文献
47.
This paper presents the application of the eMergy evaluation, introduced by H.T. Odum as an efficient methodology of environmental accounting. The results of this analysis are a part of a wider sustainability assessment for the Province of Venice realized in 2003. Within a territorial sustainability analysis, it is necessary to implement an environmental accounting method, which is able: to precisely consider the boundaries of the investigated system (spatial scale); to arbitrarily separate the life of the investigated system into periods (temporal scale); to account for both economic and natural support to a given territorial system in order to implement a sustainable management of resources; to assess all the items supporting the system on the basis of a physical unit that is objective (while the traditional economic evaluation method is based on individual preferences, hence it is subjective). The Province of Venice is a very complex system due, on one hand, to the heavy and consolidated presence of industrial activity since the beginning of the 20th century and, on the other hand, to the principal natural ecosystem which characterizes it: the lagoon, the largest wetland in the Mediterranean Sea. The role of the lagoon, as a provider of resources and services is represented by the analysis of two aspects: the lagoon as an ecosystem on the basis of the evaluation of all flows that cyclically support its biotic activity and the lagoon as a productive system on the basis of the contribution of both natural and "economic" inputs that support human activity. In particular, the case of clam fishing will be presented to put on evidence the importance of natural inputs that are systematically neglected by the traditional accounting methodologies. 相似文献
48.
Ambrosi G Dapporto P Formica M Fusi V Giorgi L Guerri A Micheloni M Paoli P Pontellini R Rossi P 《Dalton transactions (Cambridge, England : 2003)》2004,(21):3468-3474
The synthesis and characterization of two new macrocyclic ligands, the bis-macrocyclic compound 2,6-bis(1,4,13-triaza-7,10-dioxacyclopentadec-1-ylmethyl)phenol (L) and 38-methoxy-1,4,13,16,19,28-hexaaza-7,10,22,25-tetraoxatricyclo[14.14.7.1(32,36)]octatriconta-32,34,Delta(36,38)-triene (L1) are reported. Equilibrium studies of basicity and coordination properties toward metal ions such as Cu(II), Zn(II), Cd(II) and Pb(II) were performed for ligand by potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I= 0.15 mol dm(-3)). L behaves as a hexaprotic base (logK(1)= 10.93, logK(2)= 9.70, logK(3)= 8.79, logK(4)= 8.05, logK(5)= 6.83, logK(6)= 2.55). All metal ions form stable mono- and dinuclear complexes: logK(MLH(-1))= 25.61 for Cu(II), 15.37 for Zn(II), 12.58 for Cd(II) and 13.79 for Pb(II); logK(M(2)LH(-1))= 31.61 for Cu(II), 23.38 for Zn(II), 24.49 for Cd(II) and 23.68 for Pb(II). All these dinuclear species show a great tendency to add the OH(-) group: the equilibrium constant for the addition reaction was found to be logK(M(2)LH(-1)OH)= 4.77 for Cu(II), 5.66 for Zn(II), 2.8 for Cd(II) and 3.18 for Pb(II). In the case of Ni(II), kinetic inertness prevents the possibility of solution studies. The dinuclear solid adducts [Ni(2)H(-1)L(N(3))(3)].EtOH and [Cu(2)H(-1)L(N(3))](ClO(4))(2) were characterized by X-ray analysis. 相似文献
49.
Leardini R Nanni D Pareschi P Tundo A Zanardi G 《The Journal of organic chemistry》1997,62(24):8394-8399
A novel cascade radical reaction is described involving aryl isothiocyanates and 2-cyanoaryl radicals. The mechanism entails the formation of an alpha-(arylthio)imidoyl radical, a 5-exo-dig cyclization onto a cyano group, and a final 6-membered ring closure of an iminyl radical. The competitive 5-membered spiro-cyclization of the iminyl, leading to an isomeric product, was only observed in the case of a disubstituted aryl isothiocyanate. The whole process involves a rare example of [3 + 2] radical annulation and allows the one-pot synthesis of tetracondensed nitrogen heterocycles in good yields. 相似文献
50.